Nonhygroscopic sugar product



Patented Feb. 11, 1941 l PATENT OFFICE 2,231,835 NoNnYGnoscoPTc SUGAR raonnc'r James F. Walsh, Tuckahoe, N. Y., and Abraham H. Goodman, Hammond. Ind., assignors to American Maize-Products Company, ,a corporation o! Maine Application September 9, 1939, Serial No. 294,058

13 Claims.

Our invention relates to solidied, noncrystal-A line starch conversion syrup products that have a tendency to absorb moisture and cake or lump and more particularly to combinations of such products with nonhygroscopic crystalline sugars which inhibit that tendency.` This application is a continuation in part of our application Serial No. 170,764, filed October 25, 193'?.

Prior attempts to produce the solidified syrup l" product for commercial use have met with serious diiiiculties, principally becausethe dried product was hygroscopic and lumped or c'aked into a solid mass on exposure to the atmosphere. 'Ihe Syrups normally used for producing the dehydrated l5 products are obtained from starch, particularly corn starch, by well known conversion processes.

to dehydrate it to a dry solid form have resulted generally in a hygroscopic product. Furthermore, the dehydrated Solid corn syrup product has proven very diiiicult -to package and market due to this hygroscopic property. When reduced to powder form and bagged the product tends to cake or stick together to form lumps or a solid mass. This difficulty is increased the higher the .0 degree of conversion, that is, increase in amount of reducing sugars, but the caking tendency may be decreased by dehydrating the product down to a very low moisture content such as 3% or below.

The starch conversion Syrupshaving a low rebelow may bel dried satisfactorily to obtain stable nonhygroscopic products. However, these products have limited commercial value due to their low Sugar content and, accordingly very little 40 sweetness. They have poor fermentation capas bilities and generally produce cloudy viscous solur tions, or hard candies. The highest conversion products, namely, crystalline dextrose products possess the desired sweetness and will not cake 45 or become deliquescent on exposure, but they do not possess the physical properties of the solidified conversion syrup which contains dextrins in addition to the reducing sugars. The intermediate starch conversion products or sugar Syrups,

50 such as commercial corn syrup, having a reducing sugars content which is intermediate those o f the above mentioned low conversion Syrups and crystalline dextrose, are desirable in that they possess a sufli'cient amount of dextrose for sweet- 55 ness, are useful in fermentation and are substantially less expensive than the crystalline dextrose or similar nonhygroscopic crystalline sugars. However, these sugar Syrups o f intermediate reducing sugars content when solidified, possess the 60 above described disadvantages of being highly ducing Sugars content, as forexample, or

hygroscopic and therefore'dicult to maintain in a Stable nonhygroscopic dry form. Furthermore, unless they are dried to a very low moisture content such as 3% or less they will be characterized by a plastic flow of the sugar particles into each other which is conducive to lumping and caking. In accordance with the present invention we have discovered that the above difficulties may be overcome and a commercially Satisfactory Substantially dry, nonhygroscopic product having approximately any desired reducing sugars content `may be obtained by properly blending a solid, water soluble, substantially nonhygroscopic, crystalline sugar with the dried amorphous starch syrup products of various dextrose contents. The two materials may be combined in various proportions ranging from about 5% to 95% of each ingredient. Examples of Suitable solid, crystalline sugars which may be used are sucrose, dextrose, maltose hydrate and lactose. Levulose in chemically pure crystalline form may be used provided the humidity conditions 'do not exceed about 80 percent.A It is less desirable than the other Sugars mentioned because of a hygroscopic tendency and also because of its present scarcity as a commercial product. Examples of suitable starchcon'- version Syrups are the dried solidified Syrups obtained by hydrolysis of various starches such as found in corn, beans, peas, potatoes, etc.; the starch conversion Syrups being dehydrated to solid, Substantially dry form. The Starch conversion Syrup Should contain at least 20% reduclng sugars and advantageouslybetween and 65% reducing Sugars. The liquid Syrups to be dehydrated may be produced by acid, enzymatic or other suitable form of starch conversion accompanied by heat-and pressure if desired. y

We have found that when a nonhygroscopic crystalline sugar for example dextrose or sucrose is properly admixed with the dried Solidied starch conversion syrup, the reducing sugars content of which may vary over a wide range invcluding the highly hygroscopic products, the resulting product will be Substantially nonhygroscopic, and may be packaged and shipped or stored over reasonably long periods of time without caking or lumping. For example, if a starch conversion syrup, e. g. commercial corn Syrup,

.dried to a Solid form, which would be hygroscopic, and then this dried normally hygroscopic solid blended with oneof the crystalline sugars, the resulting product will be substantially nonhygroscopic and Stable. It will have practically negligible plastic flow so that it may be packaged, Stored and shipped satisfactorily without caking. The dried solidified starch conversion syrup used -in this product is not'necessarily of very low moisture content such as would. beessential if the nonhygroscopic crystalline sugar were not present. The crystalline sugar apparently has the property of taking up some of the residual moisture in the solidified starch conversion syrup and thereby preventing or inhibiting the normal plastic flow tendency of this amorphous solidied syrup. Also by blending with the solidied syrup a nonhygroscopic crystalline form oi' dextrose or other reducing sugar, the reducing sugars content of the combined product may be increased to practically any desired deg-ree without increasing the hygroscopic property. v

, If the crystalline sugar which is added to the solidiiied syrup is a reducing sugar, such as dextrose, maltose, lactose or levulose, the reducing sugars content of the combined product is increased proportionately. Thus, if it is desired to use a solidiiled syrup having a low reducing sugars content such as 35% or below, this content may be increased to practically any desired higher amount by adding to the solidiiled syrup, one of the crystalline reducing sugars. In this manner a dry product having a relatively high reducing sugars content but still being stable against caking and other hygroscopic tendencies is obtained since the addedreducing sugar is in a stable nonhygroscopic form, for example, crystalline dextrose.

If the crystalline sugar which is added tol the solidified syrup, is a nonreducing sugar, e. g. sucrose, the reducing sugars content of the combined product is proportionately decreased. The

added crystalline sucrose being a stable product will eect astabilizing` action on the normally hygroscopic solidied syrup to render the combined product stable against caking and other adverse hygroscopic properties. The amountof reducing sugars content of the finished product may vary over substantially any desired range. 'I'he reducing sugars content in the ilnai product being reduced by the sucrose, the solidiiled syrup used may have a reducing sugars content very much higher than would normally be permissible in the syrup product alone. In other words, a syrup of any desired high degree of conversion maybe made and the reducing sugars content reduced to a stable lower amount by addition of the sucrose.

Thus, as shown by the above the reducing sugars content of the solidiiled normally hygroscopic syrup may be increased or decreased over substantially any desired range by addition of the crystalline, reducing and nonreducing sugars respectively, and in all cases the hygroscopic properties of the solidified syrup reduced to a satisfactory-minimum. The increase in reducing sugars value of the solidified syrup by addition of a crystalline reducing sugar will vary in amount with the dlii'erent reducing values of` the respective sugars. For example, on a comparative basis, dextrose has a, reducing value of 'viscosity than the solidified syrup product alone due to the lower dextrin content. Microscopically our products distinguish from the solidified syrups in that they are made up of a mixture of crystals of the nonhygroscopic crystalline sugar with glassy, noncrystalllne or amorphous particles of the dehydrated solidified starch conversion syrup.

The dried solidiiled starch conversion syrups are made up primarily of dextrins, maltose and dextrose. The respective amounts of these constituents will vary with the degree of conversion of the starch from which they are made. 'Ihe dextrose content increases with increase in conversion and themaltose and dextrins decrease. A highly converted syrup therefore will contain a high percent of dextrose as compared with a syrup of low conversion.

Now, when a crystalline sugar, such as those mentioned above, is added to the solidified starch `conversion syrup, the composition of the resulting product may vary from that oi the solidified syrup both in percentage of ingredients and in kinds of ingredients. For example, if the crystalline sugar which is added to the solidified syrup, is maltose, the composition of the solidiiied syrup will be changed in percentage only since maltose is already one oi the constituents of the solidilled syrup. The added crystalline maltose will increase the percentage of maltose originally present in the solidiiled syrup. Likewise, if crystalline dextrose is addedto the solidified starch conversion syrup, vthe composition ofthe latter is changed only from a percentage standpoint since that syrup already contains dextrose as a constituent.. Accordingly, by the addition of dextrose to the solidiiled starch conversion syrup the dextrose percentage of the blended product is increased; the maltose and dextrin contents being decreased proportionately. Therefore, by the addition to the solidified syrup of a crystalline sugar which is already contained in some 'amount in that syrup, the resulting product still has only three major components, namely, dextrose, maltose and dextrins.

If the crystalline sugar which is added to the solidified syrup is not dextrose or maltose, but is nevertheless a reducing sugar such as levulose, or lactose, the reducing sugars content of the resulting product will be increased in accordance with the amount of reducing sugars added. The dextrose and maltose constituents of the solidified starchconversion syrup are reducing sugars and are normally considered together in determining the amount of reducingl sugars present in the material. Therefore, when another reducing sugar is added the total amount of reducing .sugars in the composition is increased.

I If the crystalline sugar which is added to the solidified syrup is not a reducing sugar, it will constitute a fourth component in the resulting product, that is, the product will contain dextrose, maltose, dextrins and the nonreducing sugar. An example of the latter is sucrose and as explained above, this crystalline sugar also has the property of reducing the hygroscopic tendencies of the dried solidled starch conversion syrup. When the nonreducing sugar sucrose is added to the solidiiied syrup, the amount of reducing sugar as Nvell as the dextrins actually present in the iinal product will be decreased in proportion to the amount which was originally present in the solidiiled syrup. That is, the

'fourth component sucrose, is one of the constituents in the ilnal product and decreases the Apercentage of the whole occupledby the reducing sugars, maltose and dextrose. To illustrate the percentage composition of the dried starch conversion syrup and also the percentage composinamely, dextrins, dextrose and maltose, are represented by the three different sets of intersecting lines which compose the triangle. The transverse or base lines A represent the maltose content; the oblique lines B represent the dextrin content, and the oblique lines C represent the yactual dextrose content. In this diagram the per cent of each of the three general components in the solids increases as we move in a direction approaching the respective corners thus, the amount of maltose, is shown by the base lines approaching the apex which represents 100% maltose. The lower right hand corner D of the triangle represents 100% dextrin and the lower left hand corner E represents 100% dextrose. The curved line F represents the changing compositions of various direct conversion` starch sugars, the degree of conversion increasing as we proceed along this line towards the left.

Since maltose and dextrose alone show reducing value, the dextrins being nonreducers', then it is possible to draw vertically inclined lines within the triangle shown in the drawing that will describe all possible combinations of maltose, dextrose, and conversion dextrins of equal reducing sugar values. Thus, any composition represented by any point on line G, has a 42% reducing value, the reducing sugars being calculated as though they were dextrose only as is general in this art. The poin't H represents'ordinary 42% reducing value corn syrup made by direct starch conversion which is composed of approximately 40.4% maltose, 11.6% dextrose, and 46.0% dextrins. This is the only 42% reducing value sugar of all possible compositions on line G which can be produced by direct starch conversion.

For making the' combined products of our invention we may add to the vabove described direct conversion products (compositions on curved line F) in powdered dried form, a crystalline sugar such as crystalline dextrose. The resulting sugar mixture possesses markedly improved stability 'over the direct conversion products represented by curved line F. For example, we may mix a dried sugar syrup product of 3,1% reducing sugars value with dextrose hydrate. Depending upon the amounts of each used we may prepare any composition represented in the digram by shown by linesK and L.

line I. Mixing crystalline dextrose with a dried value of about 90% which is commonly known as 70 or "80 sugar with a glass or yamorphous type of dried sugar syrup of 31% or 42% reducing value, -will permit compositions of the range The fouowing mustrativ'e but amples aregiven to illustrate further the type of nonlimiting exproducts and-procedures which characterize our invention.

. Example I In this example we dry a 42% reducing sugar corn starch conversion product in a vacuum pan and with agitation by the usual means,'until a moisture content of' about 6% or below is reached.

The resulting dehydrated syrup is then poured into pans for solidifying or is otherwise cooled. The product is a hard glass-like solid which may be fractured and powdered.

We may also dry the starch conversion syrup by other suitable means such as, for example, spray drying, in which the syrup is nely atom- -ized and is thrown into a warm current of air. The product resulting from this spray drying treatment consists .of small vitreous particles generally spherical in shape. and which fork our purposes are equally suitable and similar in action to the above described powdered product prepared by grinding. l sugar prepared as above in any suitable physical form is then mixed with the crystalline sugar. e. g. dextrose hydrate] To prepare a blended product of, for example, 60% reducing value we blend with each i100 pounds of a glassy 42% reducing sugar of 3% moisture, about 47.9 pounds dextrose hydrate crystals (water content 9.1% The crystals may be either small whole crystals or a ground powder -mad from crystals and in which the fragments are still crystalline. The blended product thus secured will be composed of 60% reducing sugars tThe glassy amorphous based upon the weight of total dry solids and will 35 contain V5% of water.

' Example II We may use crystalline anhydrous dextrose in place of .the dextrose hydrate mentioned above in the first example. Thus, to 160 pounds of the powdered .glassy 42% conversion product we.

-would add about 43.5 pounds of the anhydrous crystals. In this case the resulting product would be of 60% reducing sugar value based upon the weight of total solids and would contain 2.1%

water.

point M on the diagram and 'are composed of approximately: Per cent Dextrose (31% crystalline dextrose in mix) 42. 0 Maltese 26. 5 Dextrins 31. 5

This composition may be contrasted with a direct starch conversion product alone such as'is represented by point F in the drawing and which has approximately the following composition:v

Dextrose (0% crystalline dextrose) 29. 0 Maltose 46. 0 Dextrins 25.0

Example III We may prepare a product having 42% reducing sugars in the total solids by mixing 100 pounds of a glassy, low conversion dried sugar product of 31% reducing sugar content and about 4% water content produced by one of the conversion and drying processes described above, with about 18.1 pounds of anhydrous crystalline dextrose or with about 19.9 pounds of dextrose hydrate. These two products differ slightly `in moisture content, being about 3.4% and 4.2% respectively. 'I'he solids composition of these mixes is represented by point N on the attached drawing and consists of approximately:

. Per cent Dextrose (15.9) 22.2 Maltnse 26.5 Dextrins 51.3

This composition may be contrasted with the solids composition of a direct starch converted corn syrup alone, such as is represented by point H in the drawing and which has the approximate following composition:

Per cent Dextrose (0% crystalline dextrose) '1, 1.6 Maltose 40.4 Dextrins 48.0

the .tota-l solids present and may contain about 11% water. 'I'he mixed product will then contain about 5.4% water. In order to secure products of lower moisture content, we may pre-dry the 80 sugar below the 11% water indicated which is merely the approximate average found in this commercial product.

The mixed sugar product, which has a 42% reducing value content is different in its' properties from dried, solidified, direct converted products of this same reducing value. Particularly, it is a substantially non-hygroscopic productl whereasthe direct conversion product of 42% reducing value, when solidified,v has strong hygroscopic properties. Also, as seen from the following composition which is represented by point O in the drawing, it is different from the products Aprepared according .to the second example above:

i Per cent Dextrose (14% crystalline dextrose in mix)- 19.0

MaltOSP 30.3 Dextrins 50.7

The following examples show the preparation oi' blended products in which a crystalline sugar other than dextrose is added to the solidified starch conversion syrup.

Example IV To 100 pounds of a glassysolidied syrup hav-3 ing a 31% reducing sugars content and about 4% moisture and prepared as described above, we add about 18.1 pounds of lactose, Cul-1220111120. The resulting product has a reducing sugars value of 36.6% and contains about 4.3% Water. 'I'he percentage composition of this product would be approximately as follows:

Per cent Dextrose 6.9 Maltese 26.5 Dextrins 51.3 Lactose 15.3

Example V To 100 pounds of a glassy solidified corn syrup having about 42% reducing sugars content and about 3% moisture, is added 43.5 pounds of crystalline sucrose. The resulting product has a reducing sugars value of 29.3% and contains about 2.1% water. 'I'he percentage composition of this product would be approximately as follows:

Per cent Dextrose 8.1

Maltese 28.1

Dextrins 33.5

Sucrnse 30.3

The combined crystalline sugar and solidified amorphous starch conversion `yrup of our invention may be used in various ble products such as bakery products, candies, ice cream mixes, etc.

The term "nonhygroscopic as used in .the speciiication and claims herein to identify the products of this invention is intended to cover principally those products that are sufciently nonhygroscopic to permit packaging and storing in the ordinary mannerl without lumping or caking of Ithe material over a reasonable period of time, and are not limited to completely nonhygroscopic products that will not absorb any moisture.

It is to be understood that our invention is not groscopic sugar product comprising an intimate admixture of approximately 5% to 25% crystalline dextrose and the remainder a dried starch conversion syrup having a reducing sugars content of approximately 27% to 60%. 3. A substantially dry, water soluble, nonhygroscopic sugar product comprising an intimate admixture of approximately 5% to 25% of a crystalline conversion product having a reducing sugars value of approximately 85% to 95% and a dried amorphous glass-like sugar syrup having a reducing sugars value of approximately 27% to 4. A substantially dry, water soluble, nonhygroscopic starch conversion product comprising a blend of approximately 5% to 95% solid dextrose from' corn and approximately 95% to 5% of dried, solid, converted corn syrup.

5. A substantially drywater soluble, nonhygroscopic, starch conversion product comprising 6. A substantially dry.. water soluble, nonhygroscopic starch conversion productcomprising groscopic edible product comprising a mixture oi' about 5% to 95% oi solid crystalline sucrose and the remainder a dried solidified amorphous corn syrup containing-reducing sugars maltose and dextrose in amount of about 20%-65% and the 15 remainder principally dextrins, said sucrose being present in suflicient amount to decrease the v proportion of reducing sugars in the entire prodof about 5% to 95% oi' solid anhydrous dextrose and the remainder a dried solidified amorphous starch conversion syrup containing reducing sug- 25 ars maltose and dextrose in amount o! about 20%-65% and the remainder principally dextrins, said anhydrous dextrose being present lin suicient amount to increase the proportion of reducing sugarsin the entireproduct to a point 30 where the product is stable against plastic ilow and hygroscopic properties.

9. A substantiallydry, water soluble, nonhygroscopic edible product comprising a mixtureof about 5% to 95% of a solid, watersoluble,

35 crystalline, nonhygroscopic, sugar and the re- .L0 groscopic sugar beings-present in proper amount I to regulate the proportion'of reducing sugarsl in the entire product to a point where the product is stable against plastic now and hygroscopic properties. y

groscopic edible product` comprising a mixture o1' about 5% vto 95% comminuted, solid, crystalline nonhygroscopic sucrose and the remainder a dried solidiiied starch conversionisyrup vconl 2,231,835 a blend of approximately 5%v to 25% solid dextrose from corn and approximately 95% to '15% I of dried, solid, oonvertedrcorn syrup.

amount of about 20%-65% and` the'remainder principally dextrins, said sucrose being present in -sumcient amount to decrease the proportion of reducing sugars in the -entire product toa iiow and hygroscopic properties.

taining reducing sugars maltose and dextrose in 11. A substantially dry, water soluble, nonhygroscopic edible conversion product comprising a'mixture of about 5% to 95% comminuted, solid,

' dextrose in amount of about 20%-65% and the remainder principally dextrins, said lactose being present in suiilcient amount to increase the proportion of reducing sugars in the entirev product to a point where the product is stable against plastic now and hygroscopic properties.

12.' A substantially dry water soluble, nonhygroscopic edible product comprising an intimate4 nadmixture of a dried solidied starch conversion syrup'y containing the reducing sugars maltose and dextrose in amount of about 20% to A65% and the remainder principally dextrins, and a comminuted solid crystalline substantially'nonhygroscopic' reducing sugar which is present in ysuiiicient amount to increase-the reducing sugars content oi' the entire product to the desired extent in excess of the reducing 'sugars content in said solidied syrup but without rendering the product unstable from the standpoint of plastic now and hygroscopic properties.

13. In a substantially dry water soluble', nonhygroscoplc' edible product containing a blend of solidified starch conversion syrup and a nonhygroscopic crystalline sugar, the improvementl of increasing substantially the original amount oi reducing sugars in said product to a desired ducing sugars contentv to the desired value and 10. A substantially, dry, water soluble, nonhyj concomitantly maintains the product in a stabilized form resistant to plastic flow and hygro- 

